CN101412669B - Method for producing lactic acid by hydrothermal degradation of biomass wastes - Google Patents
Method for producing lactic acid by hydrothermal degradation of biomass wastes Download PDFInfo
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- CN101412669B CN101412669B CN2007100470628A CN200710047062A CN101412669B CN 101412669 B CN101412669 B CN 101412669B CN 2007100470628 A CN2007100470628 A CN 2007100470628A CN 200710047062 A CN200710047062 A CN 200710047062A CN 101412669 B CN101412669 B CN 101412669B
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Abstract
The invention belongs to the technical field of organic waste recycling and hydrothermal reaction, and in particular relates to a method for producing lactic acid by hydrothermally degrading biomass waste. The method comprises the following steps: in a specific hydrothermal reaction system, directly using the biomass waste as a raw material and deionized water as a solvent, and hydrothermally degrading the biomass waste at a temperature of 250 and 400 DEG C for certain reaction time to produce the lactic acid. The method realizes regulation and control of yield of the lactic acid product through changing temperature and time and adding additives.
Description
Technical field
The invention belongs to recycling organic waste and hydro-thermal reaction technical field, be specifically related to a kind of efficient, method that lactic acid is produced in environmental protection.
Background technology
Biomass are one of organic resources the abundantest on the earth, and it takes up an area of 60～80% of the biological total amount of ball.The biomass resource of China is very abundant, and only agricultural crop straw, cot are one, and annual output just reaches more than 700,000,000 ton, and wherein maize straw (35%), wheat stalk (21%) and straw (19%) are the three big stalks of China.The general in the past also form such as field, fermentation producing methane and the directly burning that acts as a fuel that adopts of the processing of agro-ecology matter waste, utilising efficiency is very low, brings a large amount of problem of environmental pollutions simultaneously.Along with the expansion and the Increase of population of city size, the domestic waste generation also increases year by year, and the present annual domestic waste total amount of China has reached 1.4 hundred million tons, and with the speed increase about 3.5%/year.The water ratio of domestic refuse Yin Qigao is handled to burning method and has been brought very big difficulty, and cultivated land resource meanwhile in short supply is unfavorable for the landfill disposal of domestic refuse.How to realize the recycling treatment of biomass wastes such as agricultural wastes and domestic waste, obtain the product of high added value, have crucial meaning.
The technology of traditional fermentative Production lactic acid is destruction, the hydrolysis that integrates biomass and ferments, the process more complicated, speed is slower, the technology that relates to is more, economic input is bigger, efficient fermenting enzyme is difficult to select, and grain consumption is huge, adopts a large amount of soda acids to bring very big inconvenience to subsequent disposal.And being equipped with lactic acid technology, acetaldehyde prussic acid legal system is restricted because of the huge toxicity of HCN.Meanwhile a large amount of biomass waste resources are not well utilized, and have produced the wasting of resources and serious environmental problem.
The chemical reaction process that it is solvent that the hydrothermal treatment consists technology is meant with overcritical and near-critical water can become macromolecule organic micromolecular compound and monomer whose or even CO in this process
2And H
2O.Water is compared with ortho-water under the hydrothermal condition, has its special nature, the density of water under hydrothermal condition, ionic product, viscosity and specific inductivity take place sharply to change, show the characteristic that is similar to dense gas, because of weakening, intermolecular hydrogen bond action cause it that organism and Gas Solubility are strengthened, the solubleness of inorganics also declines to a great extent simultaneously, these solvent natures and physical properties make it become the perfect medium of handling organic waste, the proton catalysis that takes place because of the special property of water under the hydrothermal condition, nucleophilic reaction, hydroxide ion catalysis and free radical reaction, make in the reaction process water be reaction medium be again reactant simultaneously, can play the effect of acid base catalysator under given conditions.With water is environmentally friendly solvent, can change phase behavior, rate of diffusion and solvation effect, the heterogeneous reaction that can become under the conventional solvent condition is homogeneous reaction, increase spread coefficient, reduce mass transfer and heat transmission resistance, thereby help diffusion controlled reaction, the control phase separation, shorten the reaction times, can also be used to control the distribution of product.The reactions such as oxidation, dehydration, dehydrogenation, alkylation, hydration, hydrolysis and cracking that hydrothermal condition takes place down are for its development in the field that recycling organic waste is used provides the important theoretical foundation foundation.
Hydrothermal technique has been widely used in the processing and the disposal of organic waste, and obtain good effect.Hydrothermal treatment consists recycling organic waste research now mainly is monomer, oil and the micromolecular compound of polymer degradation and the generation of hydrogen, wherein comprising polysaccharose substance degradation of small molecular compound generates, plastic cracking oiling and generation monomer, gasifying biomass system H
2Deng.
The degraded of biomass waste hydro-thermal can produce stable small molecular organic acids such as acetic acid, but the added value of acetic acid is lower, process need adds a large amount of oxygenants, and its application prospect is restricted, and the lactic acid content that traditional biomass waste hydro-thermal degraded produces is very low and unstable.
Summary of the invention
The method of the objective of the invention is to propose a kind of high-level efficiency, speed is fast, energy consumption is low, free of contamination biomass waste is produced lactic acid.
The unification that the degraded of the hydro-thermal of biomass waste can realize destroying, hydrolysis and resource utilization reclaim, it is fast that the hydro-thermal degradation process has speed, and equipment volume is little, and process range is wide, efficient height, advantages such as non-secondary pollution and conserve energy.In view of the characteristics of hydrothermal technique and the characteristic of biomass waste, the present invention utilizes the makeup of biomass waste hydrothermal resources to put, and has realized producing lactic acid by hydrothermal degradation of biomass wastes, and operating process is seen accompanying drawing 1.
The present invention adopts comparatively sophisticated hydro-thermal reaction system, directly is that reactant is realized with the biomass waste.The biomass by hydro-thermal reaction system is compared with other method of lactic acid-producing such as fermentation method and cyanide process, characteristics such as it has product output height, is swift in response, easy to operate, toxicological harmless.The consumption of the temperature of the present invention by conditioned reaction, time, reaction additives is realized the control to the resultant lactic acid production.
The method of the producing lactic acid by hydrothermal degradation of biomass wastes that the present invention proposes, its concrete steps are as follows:
A kind of method of utilizing producing lactic acid by hydrothermal degradation of biomass wastes, concrete steps are as follows:
(1) biomass waste is mixed with water, place reactor;
(2) with reactant under the stagnation point reaction conditions of water, the reaction for some time;
(3) product that obtains is filtered, obtain containing the product of lactic acid in the liquid phase.
Method as mentioned above, wherein step (1) is a reactant with particle diameter 60-200 order biomass waste, is solvent with the deionized water, places high pressure resistant, corrosion resistant reactor, the mass ratio 0.01～0.2 of reactant and solvent, the add-on of solvent are the 50-80% of reactor volume.
Method as mentioned above, wherein step (2) places the temperature control salt bath furnace with the reactor that compound is housed in the step (1), in 250 ℃ of-400 ℃ of scopes, pressure is within the 4.0-25.0Mpa scope, and kept thermostatically heating 1-10 minute with this understanding, take out reactor, at 20-40 time second internal cooling to room temperature.
Method as mentioned above, wherein step (2) places the temperature control salt bath furnace with the reactor that compound is housed in the step (1), when 250 ℃, 300 ℃ and 400 ℃ of temperature, pressure is respectively at 4.0Mpa, 9.0MPa, 25.0Mpa, with this understanding, respectively thermostatically heating is 10 minutes, 3 minutes and 1 minute, takes out reactor, at 20-40 time second internal cooling to room temperature.
Method as mentioned above, wherein step (3) is filtered the aperture of used filter membrane between 0.22-0.45 μ m.
Method wherein adds Cr in the step (1) as mentioned above
3+Additive.
Method wherein adds Cr in the step (1) as mentioned above
2(SO
4)
3Additive
Method wherein adds addition of C r in the step (1) as mentioned above
2(SO
4)
3Add-on be 0.01～2wt% of quality.
Method as mentioned above, the humidity of wherein said biomass waste is greater than 5.0%.
The invention has the advantages that:
(1) the present invention utilizes the direct degradation biological matter of hydrothermal technique waste to produce lactic acid, has broken through the traditional method of fermenting lactic acid in the past, for the generation of lactic acid provides a new approach.
(2) raw material of the present invention's employing is a biomass waste, need not utilize grain resource, when producing lactic acid, has effectively realized the processing biomass waste and has saved resource.
(3) method used in the present invention is the hydro-thermal edman degradation Edman, and the equipment of employing is simple, and required temperature is 250-400 ℃, is convenient to industry and transforms, and uses on a small quantity or does not use any additives, makes technology simpler, is convenient to the industrialization operation.
(4) the whole lactic acid-producing system of the present invention makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, and product output is high and be easy to separation, is suitable for large-scale commercial production.
(5) lactic acid of the present invention's production can be used as and can be widely used in food, pharmacy, weaving, process hides, environmental protection and the agricultural.Its product main forms is acidic flavoring agent, seasonings, sanitas, tanning agents, plant-growth regulator, Biodegradable material and chiral drug etc., and comparatively vast potential for future development and application space are arranged.
Description of drawings
Fig. 1 is biomass waste hydro-thermal degraded lactic acid producing device of the present invention.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1: the cornstalk producing lactic acid by hydrothermal degradation
(1) being reactant with particle diameter 60-200 purpose cornstalk, is solvent with the deionized water, and the mass ratio 0.01～0.2 of cornstalk and water places high pressure resistant, corrosion-resistant reactor, and the volume of water is the 50-80% of reactor volume.
(2) reactor that the compound of cornstalk and water is housed in the step (1) is placed the temperature control salt bath furnace, control reaction temperature is 250 ℃, 300 ℃ and 400 ℃, respectively under 4.0Mpa, 9.0MPa, 25.0Mpa pressure condition, and under this temperature thermostatically heating 10 minutes, 3 minutes and 1 minute respectively, take out reactor, in 30 second time, rapidly it was cooled to room temperature;
(3) products therefrom is behind 0.22-0.45 μ m membrane filtration, and liquid product is the product that contains lactic acid.
Adopt this technology can realize by the effective conversion of cornstalk to lactic product, the productive rate of lactic acid (producing the ratio of lactic acid quality and cornstalk quality) can reach more than 5.0%.
Embodiment 2: the rice husk producing lactic acid by hydrothermal degradation
Getting particle diameter 60-200 order rice husk is reactant, utilizes deionized water to be solvent, both mass ratioes 0.01～0.2, and mixture places high-pressure reactor, and the volume of water is the 50-80% of reactor volume, and other operating process is identical with embodiment 1.Utilize this method can realize becoming lactic product by the rice husk hydrothermal conversion, the productive rate of lactic acid (producing the ratio of lactic acid quality and rice husk quality) can reach more than 4.5%.
Embodiment 3: the wheat bran producing lactic acid by hydrothermal degradation
Getting particle diameter 60-200 order wheat bran is reactant, utilizes deionized water to be solvent, both mass ratioes 0.01～0.2, and mixture places high-pressure reactor, and the volume of water is the 50-80% of reactor volume, and other operating process is identical with embodiment 1.Reaction product is divided into liquid product, solid phase residue and three parts of gas, and wherein liquid phase part mainly contains lactic acid, glucose, other small molecules acid (acetic acid, formic acid etc.).Utilizing Agilent 1100 high performance liquid chromatography (U.S. Agilent company) to analyze the productive rate of lactic acid in the product as can be known (producing the ratio of lactic acid quality and wheat bran quality) to the gained liquid product can reach more than 7.4%.
Embodiment 4: there is cornstalk producing lactic acid by hydrothermal degradation down in additive
Adding particle diameter in the high-pressure reactor is 60-200 purpose cornstalk and deionized water, and both mass ratioes 0.01～0.2 add a small amount of Cr simultaneously
2(SO
4)
3Additive (the additive add-on is that the quality of 0.04% water is a reference), the volume of water is the 50-80% of reactor volume, reaction conditions is 300 ℃, 9.0MPa, the reaction times is 2 minutes, other operating process is identical with embodiment 1.Utilizing HPLC to analyze liquid product has lactic acid to generate in the product as can be known, and the productive rate of lactic acid (producing the ratio of lactic acid quality and cornstalk quality) can reach more than 9.2%.
Embodiment 5: there is rice husk producing lactic acid by hydrothermal degradation down in additive
Particle diameter is that 60-200 purpose rice husk and deionized water add in corrosion-resistant, the high pressure resistant reactor, and both mass ratioes 0.01～0.2, the volume of water are the 50-80% of reactor volume, add a small amount of Cr simultaneously
2(SO
4)
3Additive (analytical pure, Shanghai chemical reagents corporation of traditional Chinese medicines group).The additive add-on is that the quality of 0.04% water is a reference), reaction conditions is 300 ℃, 9.0MPa, the reaction times is 2 minutes, other operating process is identical with embodiment 1.Liquid product is analyzed through HPLC has lactic acid to generate as can be known, and the productive rate of lactic acid (producing the ratio of lactic acid quality and rice husk quality) can reach more than 6.7%.
Claims (8)
1. method of utilizing producing lactic acid by hydrothermal degradation of biomass wastes, it is characterized in that: concrete steps are as follows:
(1) biomass waste is mixed with water, place reactor;
(2) with reactant under the stagnation point reaction conditions of water, the reaction for some time;
(3) product that obtains is filtered, obtains containing the product of lactic acid in the liquid phase,
Step (1) is a reactant with particle diameter 60-200 order biomass waste, is solvent with the deionized water, places high pressure resistant, corrosion resistant reactor, the mass ratio 0.01～0.2 of reactant and solvent, and the add-on of solvent is the 50-80% of reactor volume.
2. method according to claim 1 is characterized in that:
Step (2) places the temperature control salt bath furnace with the reactor that compound is housed in the step (1), in 250 ℃ of-400 ℃ of scopes, pressure and kept thermostatically heating 1-10 minute with this understanding within the 4.0-25.0Mpa scope, take out reactor, at 20-40 time second internal cooling to room temperature.
3. method according to claim 1 is characterized in that:
Step (2) places the temperature control salt bath furnace with the reactor that compound is housed in the step (1), when 250 ℃, 300 ℃ and 400 ℃ of temperature, pressure is respectively at 4.0Mpa, 9.0MPa, 25.0Mpa, with this understanding, thermostatically heating is 10 minutes, 3 minutes and 1 minute respectively, take out reactor, at 20-40 time second internal cooling to room temperature.
4. method according to claim 1 is characterized in that:
Step (3) is filtered the aperture of used filter membrane between 0.22-0.45 μ m.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that: add Cr in the step (1)
3+Additive.
6. according to the described method of claim 5, it is characterized in that: add Cr in the step (1)
2(SO
4)
3Additive.
7. method according to claim 6 is characterized in that: add addition of C r in the step (1)
2(SO
4)
3Add-on be 0.01～2wt% of quality.
8. according to the described method of claim 1, the humidity that it is characterized in that described biomass waste is greater than 5.0%.
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| CN103058852B (en) * | 2013-01-25 | 2015-08-19 | 陕西师范大学 | Biomass by hydrolyzation prepares the method for lactic acid |
| CN104496784B (en) * | 2014-12-26 | 2016-05-25 | 辽宁工业大学 | The method of the auxiliary PLLA material degradation of a kind of pulse electromagnetic field |
| CN106831391A (en) * | 2017-02-27 | 2017-06-13 | 中国科学院上海高等研究院 | The method that chemicals is prepared by microalgae Direct Hydrothermal oxidation |
| CN113583694A (en) * | 2021-08-02 | 2021-11-02 | 哈尔滨伟福和安科技有限责任公司 | Rapid hydrothermal degradation treatment method for crop straws |
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| 孔令照等.超（亚）临界水热法处理有机废物的研究进展.《化工进展》.2006,第25卷(第5期),469-474. * |
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